Parameter Dependence in the Local Reaction Center Model for the Electrochemical Interface

A systematic study of OH reduction to H2O in acid electrolyte on platinum and the reverse reaction was carried out in the local reaction center model approach using B3LYP and MP2 calculations and basis sets with and without diffuse functions. It is found that the calculated electrode-potential-dependent electron transfer activation energy curves have the same general shapes and are robust toward shifts on the potential scale caused by changing the electric field at the reaction center. This opens the possibility of fixing a set of calculated activation energy curves to a single datum known from experiment and then making predictions at other potentials.